N o-dicarbamoyl-n-phenylhydroxyl-amines

ABSTRACT

NEW COMPOUNDS OF THE FORMULA:   ((X)N-PHENYL)-N(-CO-N(-R4)-R3)-OOC-N(-R1)-R2   WHEREIN EACH X IS INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HALOGEN, ALKYL, ALKENYL, HALOALKYL, NITRO, ALKOXY, ALKYLTHIO, ALKYLSULFOXIDE, ALKYLSULFONE AND DIALKYLAMINO; N IS AN INTEGER FROM 0 TO 4; R1 IS SELECTED FROM THE GROUP CONSISTING OF ALKYL, ALKENYL, HALOALKYL, AND   ((X)N-PHENYL)   WHEREIN X AND N ARE AS HERETOFORE DESCRIBED; AND R2, R3 AND R4 ARE EACH INDEPENDENTLY SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL, ALKENYL AND HALOALKYL. A HERBICIDAL AND FUNGICIDAL COMPOSITION COMPRISING AN INERT CARRIER AND AS AN ESSENTIAL ACTIVE INGREDIENT, IN A QUANTITY TOXIC TO WEEDS OR FUNGI, A COMPOUND OF THE ABOVE DESCRIPTION. A METHOD FOR THE CONTROL OF WEEDS AND FUNGI WHICH COMPRISES APPLYING TO SAID WEEDS OR FUNGI A HERBICIDAL AND FUNGICIDAL COMPOSITION COMPRISING AN INERT CARRIER AND, AS AN ESSENTIAL ACTIVE INGREDIENT, IN A QUANTITY TOXIC TO WEEDS OR FUNGI, A COMPOUND HERETOFORE DESCRIBED.

United States Patent 3,655,751 N,O-DICARBAMOYL-N-PHENYLHYDROXYL- AMINES John Krenzer, Oak Park, and Sidney B. Richter, Chicago,

Ill., assignors to Velsicol Chemical Corporation, Chicago, II]. No Drawing. Filed Jan. 3, 1968, Ser. No. 695,362 Int. Cl. C07c 127/16', 127/18, 127/20 US. Cl. 260-545 R 7 Claims ABSTRACT OF THE DISCLOSURE New compounds of the formula:

0 R1 0 ii I I R2 Kn e-rwherein each X is independently selected from the group consisting of halogen, alkyl, alkenyl, haloalkyl, nitro, alkoxy, alkylthio, alkylsulfoxide, alkylsulfone and dialkylamino; n is an integer from 0 to 4; R is selected from the group consisting of alkyl, alkenyl, haloalkyl, and

wherein X and n are as heretofore described; and R R and R are each independently selected from the group consisting of hydrogen, alkyl, alkenyl and haloalkyl. A herbicidal and fungicidal composition comprising an inert carrier and as an essential active ingredient, in a quantity toxic to weeds or fungi, a compound of the above de scription. A method for the control of weeds and fungi which comprises applying to said weeds or fungi a herbicidal and fungicidal composition comprising an inert carrier and, as an essential active ingredient, in a quantity toxic to weeds or fungi, a compound heretofore described.

This invention relates to new compositions of matter in particular this invention relates to new compounds of the formula:

9 E O C R2 sag- 0 4 3,655,751 Patented Apr. 11, 1972 wherein X and n are as heretofore described; and R R and R are each independently selected from the group consisting of hydrogen, alkyl, alkenyl and haloalkyl.

In a preferred embodiment of this invention each X is independently selected from the group consisting of chlorine, bromine, lower alkyl, lower alkenyl, lower chl oro'alkyl, lower bromoalkyl, nitro, lower alkoxy, lower al-kylthio, lower alkylsulfone, lower alkylsulfoxide and di- (lower alkyl)-amino; n is an integer from 0 to 3; R is selected from the group consisting of lower alkyl, lower alkenyl, lower haloalkyl and wherein X and n are as described; and R R and R are each independently selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower haloalkyl.

The compounds of this invention are unexpectedly useful as pesticides, particularly as herbicides and fungicides.

The new compounds of the present invention can be readily prepared by reacting a hydroxyurea of the formula:

wherein X, n, R, and R are as heretofore described with a carbamoyl chloride of the formula:

wherein R and R are as heretofore described. This reaction can be readily effected by adding the described carbamo-yl chloride to a solution of the described hydroxyurea in a suitable organic solvent, such as diethyl ether, in the presence of a base, such as triethylamine. This reaction can be conveniently performed at room temperature by stirring the reaction mixture for a period of from about /2 to about 24 hours. The desired product, which forms as a precipitate, can be readily isolated by such methods as filtration or decantation and can be used as such or can be further purified by washing, recrystallizing and the like.

Exemplary hydroxyureas which are suitable for preparing the new compounds of the present invention are 1-(3,4-dibromophenyl)-1-hydroxy-3-methylurea,

1- 3 ,4-dichlorophenyl -1-hydroxy- 3-ethylurea,

1- 2-methyl-3-chlorophenyl -1-hydroxy-3-methy1urea,

1-(3-nitro-4-methylphenyl)-1-hydroxy-3-isopropylurea,

1- 3 ,4-dichlorophenyl l-hydroxy-3 3-dimethylurea,

l- (2-methoxy-4-chlorophenyl -1-hydroxy- 3 -methylurea,

1- (4-trichloromethylphenyl -1-hydroxy-3-methylurea,

1- 3-dimethylamino-4-chlorophenyl)-1-hydroxy- 3-methylurea,

1- 4-allylphenyl) 1-hydroxy-3 ,3 -diethylurea,

1-(3,4-dichlorophenyl)-1-hydroxyurea and the like.

Exemplary suitable carbamoyl chlorides for the purpose of this invention are methylcarbamoyl chloride, ethylcarbamoyl chloride, n-propylcarbamoyl chloride, isopropylcarbamoyl chloride, dimethylcarbamoyl chloride,

diethylcarbamoyl chloride, N-ethyl-N-methylcarbamoyl chloride, N-methyl N isopropylcarbamoyl chloride, phenylcarbamoyl chloride, N-methyl-N-phenylcarbamoyl chloride, 4-methylphenylcarbamoyl chloride, 3,4-dibromophenylcarbamoyl chloride, N-methyl N (3,4-dichlorophenyl)carbamoyl chloride, 3-nitrophenylcarbamoyl chloride, 2-methoxy-4-chlorophenylcarbamoylchloride and the like.

The new compounds of this invention wherein R is.

hydrogen can also be prepared by reacting a heretofore described hydroxyurea with an isocyanate of the formula:

wherein R is as previously described. This reaction can be effected by adding the isocyanate to a solution of the hydroxyurea in a suitable organic solvent, such as diethyl ether. The presence of a catalyst, such as dibntyl tin diacetate, can greatly accelerate the reaction. The reaction can usually be performed at room temperature by stirring the reaction mixture for a period of from about 1 hour to about 24 hours. In some instances it can be desirable to reflux the reaction mixture to increase the reaction rate. The desired product forms as a precipitate and can be conveniently recovered by filtration and can be used as such or can be further purified by trituration, washing, recrystallization and the like.

Exemplary suitable isocyanates for the purpose of this invention are methyl isocyanate, ethyl isocyanate, npropyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, sec-butyl isocyanate, t-butyl isocyanate, phenyl isocyanate, 3-methylphenyl isocyanate, 4-chlorophenyl isocyanate, 3,4-difluorophenyl isocyanate, 4-iodophenyl isocyanate, 4-trifluoromethylphenyl isocyanate, 2-methyl-4- chlorophenyl isocyanate, 4-allylphenyl isocyanate, 3,4-dinitrophenyl isocyanate, 2-methoxy-4,S-dichlorophenyl isocyanate, 4-isopropylphenyl isocyanate, 3-dirnethylaminophenyl isocyanate and the like.

The manner in which the compounds of this invention can be prepared is illustrated in the following examples.

EXAMPLE 1 Preparation of 1-(3-chlorophenyl)-1-methy1- carbamoyloxy-3-methylurea A solution of l-(3-chlorophenyl)-1-hydroxy-3-rnethylurea (20 grams; 0.1 mol) in diethyl ether (200 ml.), and dibutyltin diacetate (1 drop) were charged into a glass reaction flask equipped with a mechanical stirrer. Methyl isocyanate (7 mL; 0.12 mol) was then slowly added with stirring. Stirring was continued for an additional period of about 4 hours, resulting in the formation of a precipitate. After this time, the reaction mixture was filtered to recover the precipitate. The precipitate was then recrystallized from methyl alcohol and was vacuum dried to yield 1 (3 chlorophenyl) 1 methylcarbamoy1oxy-3- methylurea as a white solid having a melting point of 144 to 145 C. and having the following elemental analysis as calculated for C H C1N O Calculated (percent): C, 46.68; H, 4.70; N, 16.32. Found (percent): C, 46.26; H, 4.64; N, 16.33.

EXAMPLE 2 Preparation of 1-(3-methylphenyl)-1-methylcarbamoyloxy-3-methylurea A solution of 1-(3-methylphenyl)-1-hydroxy-3-methylurea (12 grams; 0.07 mol) in diethyl ether (100 ml.), and dibutyltin diacetate (1 drop) were charged into a glass reaction flask equipped with a mechanical stirrer. Methyl isocyanate (7 ml.; 0.12 mol) was then slowly added with stirring. Stirring was continued for an additional period of about 4 hours, resulting in the formation of a precipitate. The precipitate was recovered by filtration and was recrystallized from methyl alcohol to yield l-(3-methylphenyl)-1-methylcarbamoyloxy 3 methylurea as a white solid having a melting point of 120 C.

.4 with decomposition and having the following elemental analysis as calculated for C I-1 N 0 Calculated (percent): C, 55.74; H, 6.36; N, 17.72. Found (percent): C, 55.36; H, 6.32; N, 17.82.

EXAMPLE 3 Preparation of 1-(3,4-dichlorophenyl)-1-methylcarbamoyloxy-3-methy1urea A solution of 1 (3,4-dichlorophenyl)-1-hydroxy-3- methylurea (12 grams; 0.05 mol) in diethyl ether (300 ml.), and dibutyltin diacetate (1 drop) were charged into a glass reaction flask equipped with a mechanical stirrer. Methyl isocyanate (3.5 ml.; 0.06 mol) was then slowly added with stirring. Stirring was continued for an additional period of about 6 hours, resulting in the formation of a precipitate. The precipitate was recovered by filtration and was recrystallized from methyl alcohol to yield 1(3,4-dichlorophenyl)-1-methylcarbamoyloxy 3 methylurea as a white solid melting at 156 C. with decomposition and having the following elemental analysis as calculated for C1QH11C12N3O3:

Calculated (percent): C, 41.11; H, 3.79; CI, 24.25. Found (percent): C, 41.50; H, 4.02; CI, 24.25.

EXAMPLE 4 Preparation of l-(3,4,5-trichlorophenyl)-1-methylcarbamoyloxy-3-methylurea A solution of 1 (3,4,5-trichlorophenyl)-1-hydroxy-3- methylurea (14.0 grams; 0.05 mol) in diethyl ether ml.), and dibutyltin diacetate (1 drop) were charged into a glass reaction flask equipped with a mechanical stirrer. Methyl isocyanate (4 ml.; 0.07 mol) was then slowly added with stirring. Stirring was continued for an additional period of about 4 hours resulting in the formation of a precipitate. The precipitate was recovered by filtration and was recrystallized from methyl alcohol to yield 1-(3,4,5 trichlorophenyl) 1 methylcarbamoyloxy-3- methylurea as a tan solid having a melting point of C. with decomposition and having the following elemental analysis as calculated for C H C1 N O Calculated (percent): C, 36.82; H, 3.09; Cl, 32.53. Found (percent): C, 36.21; H, 2.98; CI, 33.71.

EXAMPLE 5 Preparation of l-(3,4-dichlorophenyl)-1-dimethylcarbamoyloxy-3-methylurea A solution of l-(3,4 dichlorophenyl)-1-hydroxy-3- methylurea (23 grams; 0.1 mol) in diethyl ether (300 ml.), and triethylamine (18 ml.) were charged into a glass reaction flask equipped with a mechanical stirrer. Dimethylcarbamoyl chloride (11.8 grams; 0.11 mol) was then slowly added with stirring. Stirring was continued for a period of about 14 hours resulting in the formation of a precipitate. The precipitate was recovered by filtration, washed with water and recrystallized rom methyl alcohol to yield 1-(3,4-dichlorophenyl)-l-dimethylcarbamoyloxy-3-methylurea as a white solid having a melting point of 111 to 112 C. and having the following elemental analysis as calculated for C H Cl- N O Calculated (percent): C, 43.16; H, 4.28; CI, 23.16. Found (percent): C, 43.51; H, 4.63; Cl, 22.88.

EXAMPLE 6 Preparation of 1-(3,4-dichlorophenyl)-1-phenylcarbamoyloxy-3-methylurea A solution of 1-(3,4-dichlorophenyl) 1 hydroxy-3- methylurea (5 grams; 0.02 mol) in diethyl ether 100 ml.), and dibutyltin diacetate (1 drop) were charged into a glass reaction flask equipped with a mechanical stirrer and heating means. Phenyl isocyanate (2.6 grams; 0.02 ture was refluxed, with stirring, for a period of about mole) was then added to the flask and the reaction mix- 3 hours resulting in the formation of a precipitate. The precipitate was recovered by filtration, was recrystallized from methanol and vacuum dried to yield l-(3,4-dichlorophenyl)-1-phenylcarbamoyloxy-3-methylurea as a tan solid melting at 115 to 117 C. with decomposition and having the following elemental analysis as calcuated for C H Cl N O Calculated (percent): C, 50.93; H, 3.70; N, 11.87. Found (percent): C, 50.69; H, 4.04; N, 11.92.

Other compounds within the scope of this invention can be prepared by the procedure described in the foregoing examples. Presented in the following examples are the essential starting materials required to prepare the indicated named compounds according to the procedures heretofore described.

EXAMPLE 7 1 (3,4-dichlorophenyl) 1 hydroxy-3,3-dimethylurea-l-dimethylcarbamoyl chloride:1-(3,4-dichlorophenyl)-l-dimethylcarbamoyloxy-3,3-dimethylurea.

EXAMPLE 8 1-(3 methyl 4 nitrophenyl)-1-hydroxy-3-methylurea-l-methyl isocyanate=1 (3-methyl-4-nitrophenyl)-lmethylcarbamoyloxy-3-methylurea.

.EXAMPLE 9 1-(3,4 dibromophenyl)-l-hydroxy-3-methylurea+dimethylcarbamoyl chloride: 1- 3,4-dibromophenyl) -1-dimethylcarbamoyloxy-3-methylurea.

EXAMPLE 10 1-(2,6 dimethoxy-4-chlorophenyl)-l-hydroxy-3-methylurea+phenyl isocyanate=1-(2,6 dimethoxy-4-chlorophenyl)-1-phenylcarbamoyloxy-3-methylurea.

EXAMPLE 11 1(4-methy1phenyl)-1-hydroxy 3,3 dimethylurea+ 3,4-dichlorophenyl isocyanate=1-(4 methylphenyl)-1- (3,4-dichlorophenyl carbamoyloxy -3,3-dimethylurea.

EXAMPLE 12 1-(3-dimethylamino 4,5 dichlorophenyl)-1-hydroxy- 3-ethylurea-i-N-methyl-N-(4 chlorophenyl)-carbamoyl chloride:1-(3-dimethylamino 4,5 dichlorophenyl)-1- [N-methyl-N-(4 chlorophenyl)-carbamoyloxy] -3-ethylurea.

Additional compounds within the scope of this invention which can be prepared in a manner similar to that detailed in the foregoing examples but which are not to be construed as limiting this invention are and the like.

'For practical use as pesticides, the compounds of this invention are generally incorporated into pesticidal compositions which comprise an inert carrier and a pesticidally toxic amount of such a compound. Such pesticidal compositions, which can also be called formulations, enable the active compound to be applied conveniently to the site of the pest infestation in any desired quantity. These compositions can be solids such as dusts, granules,

or wettable powder; or they can be liquids such as solutions, aerosols, or emulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the active compound with a solid inert carrier such as the talcs, clays, silicas, pyrophyllite, and the like. Granular formulations can be prepared by impregnating the compound, usually dissolved in a suitable solvent, onto and into granulated carriers such as the attapulgites or the vermiculties, usually of a particle size range of from about 0.3 to 1.5 mm. Wettable powders, which can be dispersed in water or oil to any desired concentration of the active compound, can be prepared by incorporating wetting agents into concentrated dust compositions. 7

In some cases the active compounds are sufficiently soluble in common organic solvents such as kerosene or xylene so that they can be used directly as solutions in these solvents. Frequently, solutions of pesticides can be dispersed under superatmospheric pressure as aerosols. However, preferred liquid pesticidal compositions are emulsifiable concentrates, which comprise an active compound according to this invention and as the inert carrier, a solvent and an emulsifier. Such emulsifiable concentrates can be extended with water and/or oil to any desired concentration of active compound for application as sprays to the site of the pest infestation. The emulsifiers most commonly used in these concentrates are nonionic or mixtures of nonionic with anionic surface-active agents. With the use of some emulsifier systems an inverted emulsion (water in-oil) can be prepared for direct application to pest infestations.

A typical pesticidal composition according to this invention is illustrated by the following example, in which the quantities are in parts by weight.

EXAMPLE 13 Preparation of a dust Product of Example 1 10 Powdered talc The above ingredients are mixed in a mechanical grinder bIender and are ground until a homogeneous, free-flowing dust of the desired particle size is obtained. This dust is suitable for direct application to the site of the pest infestation. For the purpose of this invention the term pesticide is used to designate herbicide or fungicide.

When used as herbicides the compounds of this invention can be applied in any manner recognized by the art. One method for the control of weeds comprises contracting the locus of said weeds with a herbicidal composition comprising an inert carrier and as an essential active ingredient, in a quantity which is herbicidally toxic to said weeds, a compound of the present invention. The concentration of the new compounds of this invention in the herbicidal compositions will vary greatly with the type of formulation and the purpose for which it is designed, but generally the herbicidal compositions will comprise from about 0.05 to about percent by weight of the active compounds of this invention. In a preferred embodiment of this invention, the herbicidal compositions will comprise from about 5 to about 75 percent by Weight of the active com-pound. The compositions can also comprise such additional substances as other pesticides, such as insecticides, nematocides, fungicides, and the like; stabilizers, spreaders, deactivators, adhesives, stickers, fertilizers, activators, synergists, and the like;

The compounds of the present invention are also useful when combined with other herbicides and/or defoliants, desiccants, growth inhibitors, and the like in the herbicidal compositions heretofore described. These other materials can comprise from about 5 to about 95 percent of the active ingredients in the herbicidal compositions. Use of combinations of these other herbicides and/or defoliants, desiccants, etc. with the compounds of the present invention provide herbicidal compositions which are more eifective in controlling weeds and often provide results unattainable with separate compositions of the individual herbicides. The other herbicides, defoliants, desiccants and plant growth inhibitors, with which the compounds of this invention can be used in the herbicidal compositions to control weeds, can include chlorophenoxy herbicides such as 2,4-D, 2,4,5-T, MCPA, MCPB, 4(2,4-DB), 2,4-DEB, 4CPB, 4CPA, 4-CPP, 2,4,5-TB, 2,4,5-T-ES, 3.4-DA, silvex and the like; carbamate herbicides such as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC, and the like; thiocarbamate and dithiocarbamate herbicides such as CDEC, metham sodium, EPTC, diallate, PEBC, perbulate, vernolate and the like; substituted urea herbicides such as norea, siduron, dichloral urea, chloroxuron, cycluron, fenuron, monuron, monuron TCA, diuron, linuron, mono-linuron, neburon, buturon, trimeturon and the like; symmetrical triazine herbicides such as simazine, chlorazine, atratone, desmetryne, norazine, ipazine, prometryn, atrazine, triethazine, simetone, prometone, propazine, ametryne, and the like; chloroacetamide herbicides such as alpha-chloro- N,N-dimethylacetamide, CDEA, CDAA, alpha-chloro-N- isopropylacetamide, 2-chloro-N isopropylacetanilide, 4- (chloroacetyl) morpholine, l-(chloroacetyl) piperidine, and the like; chlorinated aliphatic acid herbicides such as TCA, dalapon, 2,3-dichloropropionic acid, 2,2,3-TPA and the like, chlorinated benzoic acid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6TBA, dicamba, tricamba, amiben, fenac, P'BA, 2-methoxy-3,6-dichlorophenylacetic acid, 3-methoxy-2,6-dichlorophenylacetic acid, 2-methoxy-3,5,6-trichlorophenylacetic acid 2,4-dichloro-3-nitrobenzoic acid and the like; and such compounds as aminotriazole, maleic hydrazide, phenyl mercuric acetate, endothal, biuret, technical chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, diquat, erbon, DNC, DNBP, dichlobenil; DPA, diphenamid, dipropalin, trifluralin, solan, dicryl, merphos, DMPA, o-S-dimethyl tetrachlorothioterephthalate, methyl 2,3,5,6-tetrachloro- N-methoxy-N-methyl terephthalarnate, 2-[(4-chloro-otolyl)-oxy]-N-methoxyacetamide, DSMA, MSMA, ptassium azide, acrolein, benefin, bensulfide, AM'S, bromacil, bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, dichlone, diphenatril, DMTT, DNAP, EBEP, EXD, I-ICA, ioxynil, IPX, isocil, potassium cyanate, MAA, MAMA, MCPES, MCPP, MH, molinate, NPA, OCH, paraquat, PCP, picloram, DPA, PCA, pyrichlor, sesone, terbacil terbutol, TCBA, brominil, CP 50144, Hl761, H-732, M-290l, sodium tetraborate, calcium cyanamid, DEF, ethyl xanthogen disulfide, sindone, sindone B, propanil and the like.

Such herbicides can also be used in the methods and compositions of this invention in the form of their salts, esters, amides, and other derivatives whenever applicable to the particular parent compounds.

Weeds are undesirable plants growing where they are not wanted, having no economic value, and interfering with the production of cultivated crops, with the growing of ornamental plants, or with the welfare of livestock. Many types of weeds are known, including annuals such as pigweed, lambsquarters, foxtail, crabgrass, wild mustard, field pennycress, ryegrass, goose-grass, chickweed, wild oats, velvet leaf, purselane, barnyard grass, smartweed. knotweed, cocklebur, wild buckwheat, kochia, medic, corn cockle, ragweed, sowthistle, coifeeweed, croton, cuphea, dodder, fumitory, groundsel, hemp nettle, knowel, spurge, spurry, emex, jungle rice, pondweed, dog fennel, carpet weed, morning glory, bedstraw, ducksalad and naiad; biennials such as wild carrot, matricaria, wild barley, campion, chamomile, burdock, mullein, roundleaved mallow, bull thistle, hounds-tongue, moth mullein, and purple star thistle; or perennials such as white cockle, perennial rye-grass, quack-grass, Johnson grass, Canada thistle, hedge bindweed, Bermuda grass, sheep sorrel, curly dock, nutgrass, field chickweed, dandelion, campanula, field bindweed, Russian knapweed, mesquite, toadflax, yarrow, aster, gromwell, horsetail, ironweed, sesbania, bulrush, cat-tail and winter-cress.

Similarly, such weeds can be classified as broadleaf or grassy weeds. It is economically desirable to control the growth of such weeds without damaging beneficial plants or livestock.

The new compounds of this invention are particularly valuable for weed control because they are toxic to many species and groups of weeds while they are relatively nontoxic to many beneficial plants. The exact amount of compound required will depend on a variety of factors, including the hardiness of the particular weed species, weather, type of soil, method of application, the kind of beneficial plants in the same area, and the like. Thus, while the application of up to only about one or two ounces of active compound per acre may be suificient for good control of a light infestation of weeds growing under adverse conditions, the application of ten pounds or more of active compound per acre may be required for good control of a dense infestation of hardy perennial weeds growing under favorable conditions.

The herbicidal toxicity of the new compounds of this invention can be illustrated by many of the established testing techniques known to the art, such as preand postemergence testing.

The herbicidal activity of the compounds of this invention was demonstrated by experiments carried out for the pre-emergence control of crabgrass, mustard Weed and pigweed. In these experiments small plastic 'greenhouse pots filled with dry soil were seeded with crabgrass, mustard and pigweed plants. Twenty four hours or less after seeding the pots were sprayed with water until the soil was wet and the test compounds formulated as aqueous emulsions of acetone solutions containing emulsifiers were sprayed at the indicated concentrations on the surface of the soil.

After spraying, the soil containers were placed in the greenhouse and provided with supplementary heat as required and daily or more frequent watering. The plants were maintained under these conditions for a period of from 15 to 21 days, at which time the condition of the plants and the degree of injury to the plants was rated on a scale of from 0 to 10, as follows: 0=no injury, 1, Z: slight injury, 3, 4=moderate injury, 5, 6==moderately severe injury, 7, 8, 9=severe injury and 10=death. The eifectiveness of these compounds is demonstrated by the following data:

The herbicidal activity of the compounds of this invention was also demonstrated by experiments carried out for the post-emergence control of mustard Weed. In these experiments the compounds to be tested were formulated as aqueous emulsions and sprayed at the indicated dosage on the foliage of mustard weed plants that had attained a prescribed size. After spraying the plants were placed in a greenhouse and watered daily or more frequently. Water was not applied to the foliage of the treated plants. The severity of the injury was determined 10 to 15 days after treatment and was rated on the scale of from 0 to 10 heretofore described. The effectiveness of these compounds is demonstrated by the following data:

The new compounds of this invention are fungicidal in their ability to kill, inhibit, or inactivate a fungus so that it does not grow. Practically, these compounds can be used to prevent fungi and molds from harming cloth, wood, plants, seeds, fruit, animals, or Whateyer else they attack. The fungicidal compound should preferably be applied before the infection has occurred and certainly before it has progressed very far.

When used as fungicides the compounds of this invention can be applied in any manner recognized by the art. The concentration of the new compounds of this invention in the fungicidal compositions will vary greatly with the type of formulation and the purpose for which it is designed, but generally the fungicidal compositions will comprise from about 0.05 to about 95 percent by weight of the active compounds of this invention. In a preferred embodiment of this invention, the fungicidal compositions will comprise from about to about 75 percent by weight of the active compound. The compositions can also comprise such additional substances as other pesticides, spreaders, adhesives, stickers, fertilizers, activators, synergists, and the like.

The compounds of the present invention are also useful when combined with other fungicides in the fungicidal compositions heretofore described. The other fungicides can comprise from about 5 to about 95 percent of the active ingredients in the fungicidal compositions. Use of combinations of these other fungicides with the compounds of the present invention provides fungicidal compositions which are more effective in controlling fungi and often provide results unattainable with separate compositions of the individual fungicides. The other fungicides, with which the compounds of this invention can be used in the fungicidal compositions to control fungi, can include fungicides such as Z-amino-butane, bordeaux mixture, ammonium dimethyl dithiocarbamate, benzoyl trimethyl ammonium bromide, cadmium sulfate, captan, chloranil, copper sulfate, cycloheximide, dichlone, 2,4 dichloro 6-(2-chloroanilino)-s-triazine, DDT, dichlone, dichloran, p-dimethylaminobenzenediazo sodium sulfonate, zinocap, diphenylmercuri 8-hydroxyquinolinate, dodine, ethylmercuric chloride, ferbam, folpet, gliodin, maneb, metham, mezineb, nabam, pentachloronitroben- Zene, PMA, phenylmercuric urea, streptomicin, thiram, zineb, ziram, difolatan, PCNB, and the like.

Such fungicides can also be used in the methods and compositions of this invention in the form of their esters, amides, and other derivatives whenever applicable to the particular parent compounds.

When the compounds of this invention are used as agricultural fungicides, they can be applied to plant foliage, to seeds, to the soil, or to such parts of plants as the fruits themselves. Plants are susceptible to a great many diseases which cause widespread damage; and among some of the more important which can be mentioned are late blight on tomato, powdery mildew on cucumber (Erisiphe cichoracearum), cereal leaf rust on wheat (Puccinia rubigo-vera), and such common soil fungi as fusarium wilt (Fusarium oxysporum), the seed rot fungus (Phythium debaranum), and the sheath and culm blight (Rhizoctonia solani). The new compounds of this invention can also be employed as industrial fungicides to control a variety of fungi which attack such materials as adhesives, cork, paints, lacquers, leather, wood, plastics, and textiles such as cotton and wool.

The quantity of active compound of this invention to be used for good disease control will depend on a variety of factors, such as the particular disease involved, the intensity of the infestation, formulation, weather, type of crop and the like. Thus, while the application of only one or two ounces of active compound per acre of a crop may be sufficient to control a light infestation of certain fungi, a pound or more of active compound per acre may be required to control a heavy infestation of a hardy species of fungus.

The fungicidal utility of the compounds of this invention was illustrated by experiments carried out for the control of leaf rust of wheat, Puccinia rubigovera. In these experiments wheat plants were grown in soil until they were about 2 to 2 /2 inches tall. The soil in which the plants were growing was then watered with about 25 cc. of a solution of the chemical in water. The plants were then placed in the greenhouse for about five days and inoculated with leaf rust spores by dusting the spores from diseased plants. After seven to ten days the growth of the fungus on the plants was measured and rated in comparison with plants inoculated but otherwise untreated. The results of these experiments are presented below.

wherein each X is independently selected from the group consisting of halogen, alkyl, alkenyl, haloalkyl, nitro, alkoxy and dialkylamino; n is an integer from O to 4; R is selected from the group consisting of alkyl, alkenyl, haloalkyl and wherein X and n have the same meaning as above; and R R and R are each independently selected from the group consisting of halogen, alkyl, alkenyl, and haloalkyl.

2. The compound of claim 1, l-(3,4-dichlorophenyl)-1- methylcarbamoyloxy-3-methylurea.

3. The compound of claim 1, 1-(3,4-dichlorophenyl)-1- dimethylcarb-amoyloxy-3-methylurea.

4. The compound of claim 1, 1-(3-chlorophenyl)-1- methylcarbamoyloxy-3-methylurea.

5. The compound of claim 1, 1-(3-methylphenyl) )-1- methylcarbamoyloxy-3-methylurea.

6. The compound of claim 1, 1-(3-,4-dichlorophenyl)- 1-phenylcarbamoyloxy-3-methylurea.

References Cited UNITED STATES PATENTS 3,192,261 6/1965 Losee et a1. 260545 3,219,428 11/1965 Weil et a1. 712.6 3,439,018 4/1969 Brooks et a1 26O471 12 FOREIGN PATENTS 182,729 6/1966 U.S.S.R. 260-545 LORRAINE A. WEINBERGER, Primary Examiner R. GERSTL, Assistant Examiner U.S. C1. X.R. 

